Bituminous compositions



Patented Aug. 29, 1956 BITUMINOUS COMPOSITIONS Denham Harman, Berkeley, and Harry J. Sommer, Corona Del Mar, Calif., assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing.

Application September 30, 1947, Serial No. 777,110

13 Claims. (01. 106-273) This invention is concerned with the preparation of bituminous compositions and is more particularly concerned with asphalt compositions and articles made therefrom having improved properties such as adhesion and, compressibility.

It is well known that bituminous substances have relatively good covering and adhesive power for dry solids such as rocks, stones, sand, cement, etc. However, it often becomes diflicultto obtain a satisfactory bond between a moist aggregate and a bituminous material such as asphalt. .Furthermore, when a solid has been coated with a bituminous substance and is subsequently exposed to water or weathering it often happens thatwater displaces the asphalt from the solid and may strip it completely.

A number of materials have been incorporated in bituminous compositions to improve their resistance .to disintegration by moisture or weathering. For .the most part, the additiveswhich have been used have been only partially successfuland their effect has been found tobe more or less temporary. For example, acidic additives such as oleophylic fatty acids improve the adhesion of certain asphalts to basic aggregates such as limestone. Various amines "and amides have been used for similar purposes but their effect is largely confined to compositions where acidic aggregates such as granite predominate. It has been noted that the efiect of any of these addi-- tives is quite specific in relation to the particular asphalt being employed. However, the greatest shortcoming which additives exhibit is their tendency to lose their adhesion effect especially when the asphalt or asphalt composition containing them is subjected to periods of heating. This is an extremely serious shortcoming since most asphalts are shipped from the refinery to a construction site in heated tank cars, or are heated at least immediately prior to their use in construction projects such as roads and like structures. Due to the specific nature of these various additives it is usually necessary for a manufacturer, refiner Or contractor to maintain a stock of various additives and to vary his compositions according to the immediate problem at hand. Usually this involves a considerable amount of testing to ascertain whether or not a specific additive or combination thereof is effective in a particular asphalt or with a specific aggregate.

It is an object of this invention to improve the adhesion of bituminous materials to solids. It is another object of this invention to provide a relatively universal adhesion agent for bituminous substances. More particularly, it is an object of this invention to provide an improved adhesion agent which is highly resistant to thermal influ ences and to abnormal'weather and mechanical stress conditions. Other objects will become evident in the following discussion.

Now, in accordance with this invention it has been found that water-insoluble polyamines obtained by hydrogenating the condensation product of an alpha-beta unsaturated aldehyde and which distinguishes these particular additives from other agents known to the prior art.

The usaturated aldehydes from which these polyamines may be prepared include those which contain an aliphatic carbon-to-carbon multiple bond interconnecting two carbon atoms, one of which is directly attached to the carbon atom of the formyl group. A particularly preferred group of unsaturated aldehydes which may be used in.

the preparation of these polyamines comprises acrolein and its homologs. The preferred group comprising these aldehydes may be defined by the structural formula omit-ps0 in whichRi represents either a hydrogen atom or an alkyl group and which may be named alphamethylene alkanols oralpha-methylene aliphatic aldehydes. This classof aldehydes among others includes acrolein, methacrolein, alpha-ethylacrolein, alpha-propylacrolein, alpha-isopropylacrolein, the alpha-butylacroleins, and their homologs which correspond to the above formula.

Aldehydes of this particular type are condensed with ammonia or amines, especially primary amines. Preferably conditions are employed wherein all of the reactants are in a liquid state, but vapor phase condensations may be used as well. The primary amines forming the most satisfactory products for use in the present inven-.

. tion include especially the aliphatic primary amines in which the alkyl group attached to the polyamines are formed; The usual hydrogenation catalysts may be used and hydrogenation may,

take place concurrently Withor's'ub's'due'ntto' the condensation.

These polyamines are usually viscous oils which;

may range in color from a light yellow to a dark 1y water-insoluble without further treatment with an organic acid.

brown, and contain carbon, nitrogen,-'and'hydro gen asfwell as up to about 10% of oxygen. The

average molecular weight of the polyam-ines gen-T erally is from' about 2 /2 to aboutfi times the molecular weight. of the unsaturated aldehyde reactant," e. g. the polyamirie's prepared from acroliriand'liquid ammonia have average molecmar weights generally within the range from atom: 1'35 to about 330. The ratio of the molec: ular weight to the equivalent" weight generally is within the range of from about 2.5; to about 4.

Thay ontain on the average more than 2 atoms ofnitrogenper molecule,; as judged'by com parison of the average molecular weight'andthe ayerage equivalent weight. These pol-yamines are thought to be composedpredominantly of complex mixtures ofhigher polyalkylene poly-' amines comprising a plurality of secondary amine nitrogen atoms and a plurality of alkyl groups and to be formed by the continued condensation of a the Lmsaturated aldehyde' with nitrogenous compounds that are formed under the -conditions described. j H I Many of these polyamines arewater-soluble or dispersible and in this form'are usually "unsuitable for use in the present compositions.- In

orderto'produce a water-insoluble additive therefrom these polyamine hydrogenated'products may be treated withan organic acid so as to form" salts or amides; Dependent upon the'solubility char"- acteristics orthe reactants and ofthe' products: so formed; the degree of reaction of the'aniino' groups'may vary within a considerable range."

For instance; as shown in Example I below, the

polyamine obtained by the hydrogenation of the condensation product of acrolein and liquid ammoniamay be water-insoluble by reaction of as little as' /g of its amino groups with a higher fatty acid such as oleic acid. It 'w-ill-be appreciated that the reaction products so obtained are ,very probably complex mixtures of salts and amides with the criterion that the substantial proportion thereof-is water insoluble; These products are easily'prepared by heating the polyamine hydrogenated'product with an organic acid at tem= peratures' between about 100 and 300 C. for periods varying from about 5 minutes to 3 hours; The products so obtaineddifier little' in appearance from the polyamine hydrogenated products but exhibit the outstanding adhesion and compression characteristics referred to above when incorporated in bituminous compositions. I

Other means may be used for insolubilizing or producing a, water-insoluble polyamine hydro; genated product; Thus, by'condensing an unsaturated" aldehyde with an amine'having anal; iphatic radical of greater than about 6 carbon atoms a product may be obtained which is usual Petroleum tars:

Typical acids which may be used for insolubil-' ization include the higher fatty acids having more than about 6 carbon atoms and especially those having greater than about lo carbon atoms, including oli c q linoleic, =afid steari'c acids among others. Additional types of acids which have been found suitable for this purpose include saturated cyclicacids such as the naphthenic acids derived fram petroleum fractions, and crude natural productssuch as tall oil.

in the specification and claims the term bitumi-nou'se substances is meant to include these materialscontaini-ng asphaltenes or tarry constituents such asthe following:

Bitumens Na tiiral-waxes: Asphalites Ozokerite Gilsonite Ceresine Glance'pitcn Montan Grahan'iite- NaturaI- asphalts' Malta asphalt Trinidadasphalt I i/renames" eel-ima- Wood tars:

Pine tar' Hardwood tar- Pyrogenous waxes Paraflin' wax Oil-gas'tar Miscellaneous tars: Ooaltarsa Pea-t tar Gas retort coal-ital" Lignite tar Low tem'perature' Shale tar: coal tar Bone tar" Pyroyenous residues Petroleum pitch Pyrogenousasphalts Oil-"gas; tar :pitch Residual oils Blown petroleum: .Coal-tar-pitdhrasphalt" Gasworlzs coal tar Soft residual; asphalt Hard residual: asphalt Sludge'asphalt.

' pitch" The solids toward which thesubject combinaationotmodinersis responsive include both'the;

acidic aggregates sueh as granite; quar-tz; and

feldspar as wellas thebasic aggregates of the limestone type, in; addition to othersurfaces such metals glass cements etc. The; sub

jeet additives have been found-to be particularly eiiective usedinconjunction-withthe sov called acidic aggregates such as silic-iousnia serials and granite. However, theyshowa satisrfactory response-with the basic types as wells: 7

- The amountofthe additive necessary to; impair-t the desireddegreepf improvement in. adhesion compression characteristicsyaries cons-id 'erably with thespecificmaterials to be needs For instance; amounts as little. as-0z25-%-by-; weight ofthe additive based upon the bituminous;

substances may; be isunicien-tin special cases When using acidie aggregates 915% is-or'dinarily satisfactory and in cases where extreme conclitions of use may be expected as much as about I stantially permanent imprevement in this-regard of thermal influences. which be encountered. Another unexpected improvement which is related'to these additions-is the substantial increase in compressive strength of bituminous compositions containing them and, furthermore, the maintenance of this characteristic in spite of adverse thermal or humidity influences. Another outstanding characteristic is the relatively universal effect which this combination has in regard to both asph-alts and aggregates. It has been found that the agents are highly effective over a very wide range of pH values beyond that normally encountered in building materials and that they are effective in substantially all types of asphalts regardless of their source. The following examples have been included to illustrate the properties of the compositions of the present invention:

Example [Ireparation of th adhesion agents hydrogen gas under a pressure of 1000 pounds per square inch at 100 C. Low boiling material, chiefly ethanol, was removed by distillation under reduced pressure, leaving 18 parts of a viscous, water-soluble oil having the following characteristics:

Molecular weight 228.00 Equivalent weight 70.00

Percent carbon 61.38 Percent nitrogen 19.25 Percent hydrogen; 10.80 Percent oxygen 8.57

The polyamine hydrogenated product 1311115011)- tained is water-soluble. In order to insolubilize it, oleic acid is heated therewith at 240 C. for minutes to form mixed reaction products principally consisting of oleic acid salts and amides of the polyamine. Three such products were prepared:

Eqfiiwgalent a 10, Additive polyaminez oleic acid These additives were employed in the tests described below:

Example I] The effect of the additives was examined by the Total Water Immersion Test as follows. using a granitic aggregate.

500 gms. of an aggregate passing 1.5 inch screen but retained by .75 inch screen is im-- mersed in water for minutes, drained and mixed for five minutes with gms. of asphalt cutback in a large porcelain dish by means of a large aluminum spoon.

The coated rock is placed in a wide mouth,

screw top, pint jar and the lid tightened. After allowing it to stand for 30 minutes, the contents or the jar are covered. with distilled water. the

lidreplaced and the jar, placed in a thermostat bath at 105 F. for3 hours. V,

At the end of this time the stones, while under water, are individually inspected, and the surface which has remained covered is estimated visually and averaged for all stones. The result is expressed ,in tenths of the surface, rounded to the nearest integer and is reported as the W. I. '1"- value. Accordingly, if the stones remain on the average 95% or more covered with the asphalt at the end of the test, the T. W. I. T. value is 10; if they remain -55% covered, the value is. 5. The results obtained are listed in the table below, together with crude sources of the several asphalts used and the concentration of the additives dissolved therein:'

Additive Source of Asphalt Additive ggfig j 32- 5;

by weight San Joaquin Valley Orude- Nona..- 2 Do 1A I 0. 5 9 1. 0 10 Example III.

Additive (concentration weight per cent) T. W. I. T.

Source of asphalt lue San 1.l)'oa(iuin Valley Crude Example IV 7 Another standard test was applied to asphalts containing som of the additives, as follows:

The retention of a continuous film of asphalt on a solid surface was tested by the following procedure:

Six parts of the asphalts listed below were mixed with parts of a soda rhyolite aggregate graded between (100% passing) and A1 (100% retained) sieves, which had 2% by weight of water on its surfaces. In each case the coating of, the aggregate was substantially complete immediately after the composition was spread out on a tin plate. After standing in open air at room temperature for one hour, the samples were covered with distilled water for 20 hours at room tempera ure. after which. the percent or r '7? asphait eoating retained on -the aggregate was estimated. The .followinE data-were-obtained:

Additive r e v v Per cent coat- Source-oiasphalt additive fg f fif f i ingret'ained' V parent on aggregate San Joaquin Valley Crude" Nnfle 5 Do A 0.5 98' 1. 100 "1.0 95 1.0 '100' 0.5 100 1.0 p 100' 1.0 100 110 100 Example V In order to determine the retention of adhesion characteristics. by the subject additives under condition simulating hot storage-or ship- ,ment, someof the samples containing additive 1 A, reported in the previous example; were' repeated, with" exception that the asphalts containing additiveswere heated for 168 hours at 121 o C. before being used to coat the aggregate. The data obtained: are given in the following table":

Source of asphalfcelitra'tion ing retained g on aggregate Example. VI

7 T he follo'wirig test demonstrates the improvement in compressive strength effected by addi- Do 1.0 100 Venezuelan Crude 0. 0 5 o.- 0.5 98 1.0 100 assua e test; described in niiampier, then-wasperformedi The results are given'in the'following' table:

No additive, 1% additive,- per cent percent Source of asphalt comp; comp.

strength strength 7 retained retained San Joaquin Valley Crude' 32 49 Gulf' Coast Orude 18 82 Venezuelan Crude 29 46 MidContinent=Cru 28- 61 Example VIII The polyamine hydrogenated product prepared asdescribed in EXampIe' 'I was heated for '15" minutes at 240 C'. with heavy naphthenicacids derived from lubricating oil stock in order to forma complex mixture of naphthenic acid salts andamides of the polyamine; a 3:1 equivalent ratio-of polyamine tonaphthenic acid being'employed Usinglthis additive, the tests-described in Examples IV and V were: repeated with the following results:

The polyarnine hydrogenated product prepared as described in Example I was heated for 15 minutes at 240 'C. with tall oil to forma complex h'ii'xture of tallroil salts and amides" of the polya'mi-ne; a 3 :1 equivalentratio of'polyamine to tall oil' beingemployed; This additive was tested as described 'i'n'Eiiamples IV and-V ing resultst' 4 r r "'0 tion of the additive LA (3:1 equivalentratio'of V 1 1 x d0 (1 Per cent Asphalt +add1- p0 yamme an 0 cm ac1 prepare as cscri e V Per'centad. coating m We heme; 168 in Examplei I. i In each case 1% by weight of -the soulce'of asphalt min-ed on gg igg g additive was incorporated-- in asphalt. aggregate on aggregate 'No'ad'diti ve; 1% additive, San Joaquin Valley percent percent' Crude 0.0 5 5 Sourceof asphalt comp. comp. D 1.0 1 strength strength Gulf O 0. 0 5 5 I retained retained D 1'. 0' 100 Venezuelan Crud v 0.0 i 5 5 p v o. 1.0 98 98 SanJoaqulnValleyCrude" a2 59 60 Mid-Continent Crude. 0.0 5 5 Gulf Coast orude 1s- 56' Do 1. 0 9s 90 Venezuelan Crude 29 52 Mid-Continent Crude; 28' 50 e The Retention"of' 'St-rength 'Iest employedin Example VII In order to determine-the: ability of" the subject combination" of. additives". to-mainta'i'n: their efiecti'veness over long perio'd's of -heating; suchas would occur during-shipment to" a construction site;- the following test was 7 performed:

The samples d-es cribe'd in' Example VI were du plieated except -thatzthe asphalt, after the ad dition 'oi' additives, 'wasiheld: at a: temperature- 0f 25o F.rfor 163. hours before the 1 testcylinders were-meda The compression strength retention obtaining the data reported in Examplesvl and VII is as follows:

In each case-l parflbjrweight' off the additive IA wasin'c'orp'orated in 100 parts by weight'of" and 4' inches in Ieng th 'by applicatio'n ofa load on both endsof thesam'ple for '1 of 1500p; s. i minutcg with the follow- The resultingmixture was Duplicate samples were prepared; one was tested for compressive strength without further treatment and a second was immersed for 3 days in water and then tested for compressive strength. The compressive strengths of the first two comparative samples were compared and the results reported are the percentages of the original strength retained after the water soaking.

The compressive strength was tested by placing the cylinder on end and applying a downward load at a rate of one inch per minute until the cylinder disintegrates. The maximum pressure recorded by the testing machine was taken as the compressive strength. The data obtained are given, together with comparative data from samples containing no additives.

We claim as our invention:

1. A bituminous composition having improved adhesion and compression characteristics comprising a major amount of an asphalt and 0.5-% by weight of a water-insoluble material obtained by reacting a substance selected from the group consisting of ammonia and an aliphatic primary amine having 124 carbon atoms with an alphamethylene alkanal at a temperature between 70 C. and +150 C., hydrogenating the resulting reaction product and reacting the hydrogenated reaction product with an organic carboXylic acid having more than 6 carbon atoms to produce said water-insoluble material.

2. A bituminous composition having improved adhesion and compression characteristics comprising a major amount of an asphalt and 0.5-5% by weight of a product obtained by treating acrolein with ammonia at 60 to 70 C., removing excess ammonia, hydrogenating the reaction product, and heating the hydrogenated reaction product with 1-3 equivalent weights of a fatty acid having more than 6 carbon atoms at 100 to 300 C. for 5 to 180 minutes.

3. A composition according to claim 2 wherein the fatty acid is oleic acid.

4. A composition according to claim 2 wherein said hydrogenated reaction product and fatty acid are heated together for a period of 15 minutes at 240 C.

5. A bituminous composition having improved adhesion and compression characteristics comprising a major amount of an asphalt and 0.5-5% by weight of a product obtained by treating ammonia with an alpha-methylene alkanal at a temperature between -70 C. and. +150 C., removing excess ammonia, hydrogenating the reaction product and heating the hydrogenated reaction product with 1-3 equivalent weights of a fatty acid having more than 6 carbon atoms at 100 C. to 300 C. for 5 to 180 minutes.

6. A bituminous composition having improved adhesion and compression characteristics comprising a major amount of an asphalt and 0.5-5% by weight of a product obtained by treating an aliphatic primary amine having 1 24 carbon atoms with an alpha-methylene alkanal at a temperature between C. and +150 C., removing excess amine and hydrogenating the reaction product and reacting the hydrogenated reaction product with an organic carboxylic acid having more than 6 carbon atoms to produce a water-insoluble product.

7. A bituminous composition having improved adhesion and compression characteristics comprising a major amount of an asphalt and 0.5-5% by weight of a product obtained by treating ammonia with acrolein at a temperature between 70 C. and +150 0., removing excess ammonia, hydrogenating the reaction product and heating the hydrogenated reaction product with 1-3 equivalent weights of an organic carboxylic acid having more than 6 carbon atoms at a temperature of C. to 300 C. for 5 to 180 minutes.

8. A bituminous composition according to claim 7, wherein the organic acid is a mixture of petroleum naphthenic acids.

9. A bituminous composition according to claim '7, wherein the organic acid is tall oil.

10. A composition according to claim 5 wherein the product obtained by treating ammonia with the alpha-methylene alkanal has a molecular weight from about 2.5 to about 6 times the molecular weight of said alkanal.

11. A composition according to claim 7 wherein the product obtained by treating ammonia with acrolein has a molecular weight between about and about 330.

12. A composition according to claim 1 wherein the organic carboxylic acid has more than 10 carbon atoms.

13. A composition according to claim 1 wherein the water-insoluble material is present in an amount of 1-3% by weight.

DENHAM HARMAN. HARRY J. SOMMER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,674,523 Sadtler June 19, 1928 2,191,295 Dohse et al Feb. 20, 1940 2,386,867 Johnson Oct. 16, 1945 2,426,220 Johnson Aug. 26, 1947 FOREIGN PATENTS Number Country Date 568,385 Great Britain Apr. 3, 1945 847,829 Great Britain July 10, 1939 

1. A BITUMINOUS COMPOSITION HAVING IMPROVED ADHESION AND COMPRESSION CHARACTERISTICS COMPRISING A MAJOR AMOUNT OF AN ASPHALT AND 0.5-5% BY WEIGHT OF A WATER-INSOLUBLE MATERIAL OBTAINED BY REACTING A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF AMMONIA AND AN ALIPHATIC PRIMARY AMINE HAVING 1-24 CARBON ATOMS WITH AN ALPHAMETHYLENE ALKANAL AT A TEMPERATURE BETWEEN -70*C. AND +150*C., HYDROGENATING THE RESULTING REACTION PRODUCT AND REACTING THE HYDROGENATED REACTION PRODUCT WITH AN ORGANIC CARBOXYLIC ACID HAVING MORE THAN 6 CARBON ATOMS TO PRODUCE SAID WATER-INSOLUBLE MATERIAL. 